US20240182393A1 - Selective catalytic alkene isomerization for making fragrance ingredients or intermediates - Google Patents
Selective catalytic alkene isomerization for making fragrance ingredients or intermediates Download PDFInfo
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- US20240182393A1 US20240182393A1 US18/282,838 US202218282838A US2024182393A1 US 20240182393 A1 US20240182393 A1 US 20240182393A1 US 202218282838 A US202218282838 A US 202218282838A US 2024182393 A1 US2024182393 A1 US 2024182393A1
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- US
- United States
- Prior art keywords
- mol
- ruthenium
- alkene
- catalyst
- terminal alkene
- Prior art date
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- 150000001336 alkenes Chemical class 0.000 title claims abstract description 135
- 239000003205 fragrance Substances 0.000 title claims abstract description 20
- 239000004615 ingredient Substances 0.000 title claims abstract description 12
- 238000006317 isomerization reaction Methods 0.000 title description 38
- 239000000543 intermediate Substances 0.000 title description 10
- 230000003197 catalytic effect Effects 0.000 title 1
- 239000003054 catalyst Substances 0.000 claims abstract description 126
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 111
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 107
- 238000000034 method Methods 0.000 claims abstract description 77
- 230000008569 process Effects 0.000 claims abstract description 68
- 239000007858 starting material Substances 0.000 claims abstract description 40
- 239000002904 solvent Substances 0.000 claims description 29
- NNWHUJCUHAELCL-SNAWJCMRSA-N trans-isomethyleugenol Chemical group COC1=CC=C(\C=C\C)C=C1OC NNWHUJCUHAELCL-SNAWJCMRSA-N 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 26
- 239000004912 1,5-cyclooctadiene Substances 0.000 claims description 23
- 239000012327 Ruthenium complex Substances 0.000 claims description 21
- NNWHUJCUHAELCL-UHFFFAOYSA-N cis-Methyl isoeugenol Natural products COC1=CC=C(C=CC)C=C1OC NNWHUJCUHAELCL-UHFFFAOYSA-N 0.000 claims description 15
- ZYEMGPIYFIJGTP-UHFFFAOYSA-N O-methyleugenol Chemical group COC1=CC=C(CC=C)C=C1OC ZYEMGPIYFIJGTP-UHFFFAOYSA-N 0.000 claims description 14
- 150000003303 ruthenium Chemical class 0.000 claims description 14
- WIWBLJMBLGWSIN-UHFFFAOYSA-L dichlorotris(triphenylphosphine)ruthenium(ii) Chemical compound [Cl-].[Cl-].[Ru+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 WIWBLJMBLGWSIN-UHFFFAOYSA-L 0.000 claims description 12
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 9
- 229910019891 RuCl3 Inorganic materials 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229940116837 methyleugenol Drugs 0.000 claims description 7
- PRHTXAOWJQTLBO-UHFFFAOYSA-N methyleugenol Natural products COC1=CC=C(C(C)=C)C=C1OC PRHTXAOWJQTLBO-UHFFFAOYSA-N 0.000 claims description 7
- QGFSQVPRCWJZQK-UHFFFAOYSA-N 9-Decen-1-ol Chemical group OCCCCCCCCC=C QGFSQVPRCWJZQK-UHFFFAOYSA-N 0.000 claims description 6
- BPKHQNOYGCYSNX-UHFFFAOYSA-N 4-ethylidene-2-propoxycyclohexan-1-ol Chemical compound CCCOC1CC(CCC1O)=CC BPKHQNOYGCYSNX-UHFFFAOYSA-N 0.000 claims description 5
- GRIJJFXIWPYPSR-UHFFFAOYSA-N 5-ethenyl-2-propoxycyclohexan-1-ol Chemical compound C(CC)OC1C(CC(CC1)C=C)O GRIJJFXIWPYPSR-UHFFFAOYSA-N 0.000 claims description 5
- GIZPOCVFOCTZBV-UHFFFAOYSA-N 5-ethylidene-2-propoxycyclohexan-1-ol Chemical compound C(C)=C1CCC(C(C1)O)OCCC GIZPOCVFOCTZBV-UHFFFAOYSA-N 0.000 claims description 5
- WBKSXWUCPDFXMN-UHFFFAOYSA-N 4-ethenyl-2-propoxycyclohexan-1-ol Chemical compound C(CC)OC1C(CCC(C1)C=C)O WBKSXWUCPDFXMN-UHFFFAOYSA-N 0.000 claims description 4
- POYBJJLKGYXKJH-PHFPKPIQSA-N (1z,5z)-cycloocta-1,5-diene;2-methanidylprop-1-ene;ruthenium(2+) Chemical compound [Ru+2].CC([CH2-])=C.CC([CH2-])=C.C\1C\C=C/CC\C=C/1 POYBJJLKGYXKJH-PHFPKPIQSA-N 0.000 claims description 3
- GBSLQEKRRMETIB-UHFFFAOYSA-N dec-6-en-1-ol Chemical compound CCCC=CCCCCCO GBSLQEKRRMETIB-UHFFFAOYSA-N 0.000 claims description 2
- JPYLHKPRBLLDDJ-UHFFFAOYSA-N dec-7-en-1-ol Chemical compound CCC=CCCCCCCO JPYLHKPRBLLDDJ-UHFFFAOYSA-N 0.000 claims description 2
- USAHNNPOSAWOSH-UHFFFAOYSA-N dec-8-en-1-ol Chemical compound CC=CCCCCCCCO USAHNNPOSAWOSH-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 46
- 239000000047 product Substances 0.000 description 25
- 239000003446 ligand Substances 0.000 description 19
- 230000035484 reaction time Effects 0.000 description 17
- 239000002253 acid Substances 0.000 description 16
- 239000000654 additive Substances 0.000 description 14
- 230000000996 additive effect Effects 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 230000008901 benefit Effects 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 6
- -1 ruthenium coordination complex Chemical class 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 150000003304 ruthenium compounds Chemical class 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- NQZFAUXPNWSLBI-UHFFFAOYSA-N carbon monoxide;ruthenium Chemical group [Ru].[Ru].[Ru].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] NQZFAUXPNWSLBI-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- KSMVZQYAVGTKIV-UHFFFAOYSA-N decanal Chemical compound CCCCCCCCCC=O KSMVZQYAVGTKIV-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910017147 Fe(CO)5 Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000002518 distortionless enhancement with polarization transfer Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- ZRPFJAPZDXQHSM-UHFFFAOYSA-L 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazole;dichloro-[(2-propan-2-yloxyphenyl)methylidene]ruthenium Chemical compound CC(C)OC1=CC=CC=C1C=[Ru](Cl)(Cl)=C1N(C=2C(=CC(C)=CC=2C)C)CCN1C1=C(C)C=C(C)C=C1C ZRPFJAPZDXQHSM-UHFFFAOYSA-L 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- PNPBGYBHLCEVMK-UHFFFAOYSA-N benzylidene(dichloro)ruthenium;tricyclohexylphosphanium Chemical compound Cl[Ru](Cl)=CC1=CC=CC=C1.C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1.C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1 PNPBGYBHLCEVMK-UHFFFAOYSA-N 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- DHCWLIOIJZJFJE-UHFFFAOYSA-L dichlororuthenium Chemical compound Cl[Ru]Cl DHCWLIOIJZJFJE-UHFFFAOYSA-L 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 150000004820 halides Chemical group 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- WUFCFZZEXGODEL-UHFFFAOYSA-N n-diphenylphosphanyl-n-methylmethanamine Chemical compound C=1C=CC=CC=1P(N(C)C)C1=CC=CC=C1 WUFCFZZEXGODEL-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 229910009112 xH2O Inorganic materials 0.000 description 2
- VUNFOJWKJSYIDH-VOTSOKGWSA-N (e)-dec-4-en-1-ol Chemical compound CCCCC\C=C\CCCO VUNFOJWKJSYIDH-VOTSOKGWSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- WYPQHXVMNVEVEB-AATRIKPKSA-N 5-decen-1-ol Chemical compound CCCC\C=C\CCCCO WYPQHXVMNVEVEB-AATRIKPKSA-N 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- GKULYWPYMHSGTM-UHFFFAOYSA-N COC1=C(C=C(C=C1)CC=C)OC.CC1=C(C(=CC(=C1)CC=C)OC)O Chemical compound COC1=C(C=C(C=C1)CC=C)OC.CC1=C(C(=CC(=C1)CC=C)OC)O GKULYWPYMHSGTM-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 229910004039 HBF4 Inorganic materials 0.000 description 1
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910003244 Na2PdCl4 Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical class CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- ROZSPJBPUVWBHW-UHFFFAOYSA-N [Ru]=O Chemical class [Ru]=O ROZSPJBPUVWBHW-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- PNPBGYBHLCEVMK-UHFFFAOYSA-L benzylidene(dichloro)ruthenium;tricyclohexylphosphane Chemical compound Cl[Ru](Cl)=CC1=CC=CC=C1.C1CCCCC1P(C1CCCCC1)C1CCCCC1.C1CCCCC1P(C1CCCCC1)C1CCCCC1 PNPBGYBHLCEVMK-UHFFFAOYSA-L 0.000 description 1
- FCDPQMAOJARMTG-UHFFFAOYSA-M benzylidene-[1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene]-dichlororuthenium;tricyclohexylphosphanium Chemical compound C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1.CC1=CC(C)=CC(C)=C1N(CCN1C=2C(=CC(C)=CC=2C)C)C1=[Ru](Cl)(Cl)=CC1=CC=CC=C1 FCDPQMAOJARMTG-UHFFFAOYSA-M 0.000 description 1
- CCDWGDHTPAJHOA-UHFFFAOYSA-N benzylsilicon Chemical compound [Si]CC1=CC=CC=C1 CCDWGDHTPAJHOA-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- MLIYPCQSOXNTLJ-UHFFFAOYSA-N carbon monoxide;ruthenium dihydride;triphenylphosphane Chemical compound [RuH2].[O+]#[C-].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 MLIYPCQSOXNTLJ-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- BJNVYFXBTNBKRU-UHFFFAOYSA-L dichlororuthenium;2-diphenylphosphanylethanamine Chemical compound Cl[Ru]Cl.C=1C=CC=CC=1P(CCN)C1=CC=CC=C1.C=1C=CC=CC=1P(CCN)C1=CC=CC=C1 BJNVYFXBTNBKRU-UHFFFAOYSA-L 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 150000002835 noble gases Chemical class 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical class [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- GTBPUYSGSDIIMM-UHFFFAOYSA-N phosphane;ruthenium Chemical class P.[Ru] GTBPUYSGSDIIMM-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920001921 poly-methyl-phenyl-siloxane Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- LECPYKYNIWHZFT-UHFFFAOYSA-K ruthenium(3+) triperchlorate Chemical class [Ru+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O LECPYKYNIWHZFT-UHFFFAOYSA-K 0.000 description 1
- WYRXRHOISWEUST-UHFFFAOYSA-K ruthenium(3+);tribromide Chemical class [Br-].[Br-].[Br-].[Ru+3] WYRXRHOISWEUST-UHFFFAOYSA-K 0.000 description 1
- ARSLWGHFZUGJTK-UHFFFAOYSA-K ruthenium(3+);trifluoromethanesulfonate Chemical class [Ru+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F ARSLWGHFZUGJTK-UHFFFAOYSA-K 0.000 description 1
- LJZVDOUZSMHXJH-UHFFFAOYSA-K ruthenium(3+);triiodide Chemical class [Ru+3].[I-].[I-].[I-] LJZVDOUZSMHXJH-UHFFFAOYSA-K 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/32—Preparation of ethers by isomerisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B35/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving a change in the type of bonding between two carbon atoms already directly linked
- C07B35/08—Isomerisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/56—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by isomerisation
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B9/00—Essential oils; Perfumes
- C11B9/0007—Aliphatic compounds
- C11B9/0015—Aliphatic compounds containing oxygen as the only heteroatom
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B9/00—Essential oils; Perfumes
- C11B9/0061—Essential oils; Perfumes compounds containing a six-membered aromatic ring not condensed with another ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/09—Geometrical isomers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0046—Ruthenium compounds
Definitions
- the present disclosure relates to a selective alkene isomerization process to convert a terminal alkene to an internal alkene by using a ruthenium catalyst and more particularly to a process for making fragrance ingredient or fragrance intermediate.
- Alkene isomerization reactions have been identified as one of the key transformations that affords either final fragrance ingredients or valuable synthetic intermediates. However, each of these processes require different catalyst and conditions. Furthermore, isomerizations need to provide maximum conversion and be highly selective. Structural differences among starting material, desired final product and isomeric byproducts are in certain cases minimal, making final purification and/or isolation challenging due to the very similar physicochemical properties.
- homogeneous Lewis acid catalysts are commonly employed in the Fine Chemical Industry for double bond isomerization reactions.
- Alternative catalysts include solid acid catalysts containing Brönsted, Lewis or both type of acid centers (for selected examples see: J. Catal. 1962, 1, 2231; EP211985A1; EP442159B1; US20150141720A1) such as sulfated-zirconias, metal (usually Pt) supported zeolites heteropolyacids, molybdenum oxides, Al 2 O 3 -TiO 2 and alkali exchanged (X type) or alumina doped (K, Na, Cs . . .) zeolites (see, for instance, U.S. Pat. No.
- the present disclosure provides an isomerization process for making fragrance ingredient or fragrance intermediate.
- the process converts a terminal alkene to an internal alkene and comprises isomerizing a starting material comprising a terminal alkene to form a product comprising an internal alkene in the presence of a ruthenium catalyst at a temperature of at least about 120° C. in a reaction zone.
- FIG. 1 shows molecular structures of some ruthenium complexes.
- the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion.
- a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
- “or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
- the recited range should be construed as including ranges “1 to 8”, “3 to 10”, “2 to 7”, “1.5 to 6”, “3.4 to 7.8”, “1 to 2 and 7-10”, “2 to 4 and 6 to 9”, “1 to 3.6 and 7.2 to 8.9”, “1-5 and 10”, “2 and 8 to 10”, “1.5-4 and 8”, and the like.
- compositions and methods are described herein in terms of “comprising” various components or steps, the compositions and methods also can “consist essentially of” or “consist of” the various components or steps, unless stated otherwise.
- alkene molecules may exist as cis or trans stereoisomers.
- an alkene molecule, structure, formula, or chemical name
- an alkene as used herein includes both cis and trans stereoisomers, as well as any combinations or mixtures of the cis and trans stereoisomers.
- terminal alkene means a molecule comprising an organic moiety represented by Formula I set forth below:
- the double bond is on a terminal carbon.
- internal alkene means a molecule comprising a double bond which is not on the terminal carbon.
- the internal alkene means a molecule comprising an organic moiety represented by Formula II set forth below:
- the terminal alkene is a molecule comprising an organic moiety represented by Formula III set forth below wherein n is an integer from 1 to 20:
- the internal alkene is a molecule comprising an organic moiety represented by Formula IV, or a molecule comprising an organic moiety represented by Formula V, or mixtures of molecules of Formula IV and Formula V, as shown below:
- n is an integer from 1 to 15, or an integer from 1 to 10. In some embodiments, n is 1.
- Terminal alkene in this disclosure is a primary alkene, that is, the double bond is only connected to one carbon.
- secondary alkene means a molecule comprising a double bond which is connected to two carbons.
- tertiary alkene as used herein, means a molecule comprising a double bond which is connected to three carbons.
- quaternary alkene as used herein, means a molecule comprising a double bond which is connected to four carbons. A double bond in an aromatic functional group is not deemed as the kind of double bond referred to above in the definition of the terms secondary alkene, tertiary alkene and quaternary alkene.
- ruthenium complex means a ruthenium coordination complex comprising a central ruthenium atom or cation surrounded by one or more coordination ligands that bind to the central ruthenium atom or cation.
- the bonding with the ruthenium atom or cation generally involves formal donation of one or more of the ligand's electron pairs.
- yield of the internal alkene means the total molar amount of the internal alkene (product) formed in the isomerizing process (reaction) comparing with the total molar amount of the terminal alkene (starting material).
- fragment intermediate means an intermediate molecule (e.g., formed during multiple-step chemical reactions) which can react or be transformed to provide a final molecule which can be used as a fragrance ingredient.
- a terminal alkene starting material is converted by an isomerization reaction to an internal alkene product.
- the terminal alkene starting material and the internal alkene product are position isomers, that is, they are different only on the position of the double bond.
- the isomerization process can be conducted by contacting a starting material comprising a terminal alkene with a ruthenium catalyst in a reaction zone.
- the starting material comprises at least 80 wt %, or at least 85 wt %, or at least 90 wt %, or at least 95 wt %, or at least 98 wt %, or at least 99 wt % of the terminal alkene based on the total weight of the starting material.
- the starting material consists essentially of or consists of the terminal alkene.
- the starting material comprises no more than 10 mol %, or no more than 5 mol %, or no more than 2 mol %, or no more than 1 mol %, or no more than 0.5 mol %, or no more than 0.2 mol %, or no more than 0.1 mol %, or no more than 0.05 mol %, or no more than 0.02 mol %, or no more than 0.01 mol % of a secondary alkene based on the total molar amount of the starting material.
- the starting material is substantially free or free of a secondary alkene.
- the starting material comprises no more than 10 mol %, or no more than 5 mol %, or no more than 2 mol %, or no more than 1 mol %, or no more than 0.5 mol %, or no more than 0.2 mol %, or no more than 0.1 mol %, or no more than 0.05 mol %, or no more than 0.02 mol %, or no more than 0.01 mol % of a tertiary alkene based on the total molar amount of the starting material.
- the starting material is substantially free or free of a tertiary alkene.
- the starting material comprises no more than 10 mol %, or no more than 5 mol %, or no more than 2 mol %, or no more than 1 mol %, or no more than 0.5 mol %, or no more than 0.2 mol %, or no more than 0.1 mol %, or no more than 0.05 mol %, or no more than 0.02 mol %, or no more than 0.01 mol % of a quaternary alkene based on the total molar amount of the starting material.
- the starting material is substantially free or free of a quaternary alkene.
- the terminal alkene molecule can comprise one or more functional groups containing oxygen and/or halide atoms. In some embodiments, the terminal alkene molecule comprises one or more functional groups selected from the group consisting of alkyl, aryl, alkoxy, hydroxy, halide and ester. In some embodiments, the terminal alkene molecule comprises one or more functional groups selected from the group consisting of alkyl, aryl, alkoxy and hydroxy.
- the terminal alkene molecule does not comprise nitrogen element. In some embodiments, the terminal alkene molecule does not comprise an organic basic group. In some embodiments, the terminal alkene molecule does not comprise an amine functional group.
- a starting material comprising a terminal alkene is isomerized to form a product comprising an internal alkene in the presence of a ruthenium catalyst.
- the ruthenium catalyst is a ruthenium-containing catalyst which catalyzes the positional isomerization of the terminal alkene. Unless explicitly indicated, the ruthenium catalyst is not supported on a catalyst support or carrier. In some embodiments, the ruthenium catalyst is selected from the group consisting of ruthenium complexes, ruthenium salts, ruthenium in metal form, and mixtures thereof.
- the ruthenium complexe is selected from the group consisting of ruthenium alkene complexes, ruthenium carbonyl complexes, ruthenium phosphine complexes, and mixtures thereof.
- the ruthenium salt is selected from the group consisting of ruthenium chlorides, ruthenium bromides, ruthenium iodides, ruthenium oxides, ruthenium triflates, ruthenium perchlorates, and mixtures thereof. Ruthenium salts can be in anhydrous or hydrated form. Examples of ruthenium in metal form include ruthenium black.
- ruthenium is in an oxidation state of 0, II or III in a ruthenium catalyst.
- the ruthenium catalyst comprises no more than 20 wt %, or no more than 15 wt %, or no more than 10 wt %, or no more than 5 wt %, or no more than 1 wt %, or no more than 0.2 wt %, or no more than 0.1 wt %, or no more than 0.05 wt %, or no more than 0.02 wt %, or no more than 0.01 wt % of a ruthenium compound having oxidation state of IV or higher based on the total weight of the ruthenium catalyst.
- the ruthenium catalyst is substantially free or free of a ruthenium compound having oxidation state of IV or higher.
- the ruthenium complex is selected from the group consisting of bis(2-methylallyl)(1,5-cyclooctadiene)ruthenium(II) complex (Ru(methylallyl) 2 (COD)), dichlorotris(triphenylphosphine)ruthenium(II) complex (RuCl 2 (PPh 3 ) 3 ), dichlorobis( 2 -(diphenylphosphino)ethylamine)ruthenium(II) complex (RuCl 2 (C 14 H 16 NP) 2 ), carbonyldihydridotris(triphenylphosphine)ruthenium(II) complex (Ru(CO)H 2 (PPh 3 ) 3 ), triruthenium dodecacarbonyl complex (Ru 3 (CO) 12 ), dichloro(benzylidene)bis(tricyclohexylphosphine)ruthenium(II) complex (Grubbs 1 st generation), dichlor
- the ruthenium complex is selected from the group consisting of bis(2-methylallyl)(1,5-cyclooctadiene)ruthenium(II) complex (Ru(methylallyl) 2 (COD)), dichlorotris(triphenylphosphine)ruthenium(II) complex (RuCl 2 (PPh 3 ) 3 ), and mixtures thereof.
- the ruthenium complex is dichlorotris(triphenylphosphine)ruthenium(II) complex.
- the ruthenium complex is fully dissolved in the terminal alkene starting material under the process or reaction conditions in this disclosure. In some embodiments, at least 70 wt %, or at least 80 wt %, or at least 85 wt %, or at least 90 wt %, or at least 95 wt %, or at least 98 wt % of the ruthenium complex used in the process (based on the total weight of the ruthenium complex used in the process) is dissolved in the terminal alkene starting material under the process or reaction conditions.
- the ruthenium salt is RuCl 3 (anhydrous and/or hydrated). In some embodiments, the ruthenium salt is essentially insoluble in the terminal alkene starting material under the process or reaction conditions in this disclosure. In some embodiments, the solubility of the ruthenium salt is no more than 30 wt %, or no more than 20 wt %, or no more than 15 wt %, or no more than 10 wt %, or no more than 5 wt %, or no more than 2 wt %, or no more than 1 wt %, or no more than 0.5 wt %, or no more than 0.2 wt %, or no more than 0.1 wt %, or no more than 0.05 wt %, or no more than 0.02 wt %, or no more than 0.01 wt % (based on the total weight of the ruthenium salt used in the process) in the terminal alkene starting material under the process or reaction
- the amount of the ruthenium catalyst is at least 0.0001 mol %, or at least 0.0002 mol %, or at least 0.0005 mol %, or at least 0.001 mol %, or at least 0.002 mol %, or at least 0.005 mol %, or at least 0.01 mol %, or at least 0.02 mol %, or at least 0.05 mol % based on the total molar amount of the terminal alkene.
- the amount of the ruthenium catalyst is no more than 1 mol %, or no more than 0.8 mol %, or no more than 0.5 mol %, or no more than 0.4 mol %, or no more than 0.3 mol %, or no more than 0.2 mol %, or no more than 0.15 mol %, or no more than 0.1 mol % based on the total molar amount of the terminal alkene.
- the ruthenium catalyst is a ruthenium complex and the amount of the ruthenium catalyst is at least 0.0001 mol %, or at least 0.0002 mol %, or at least 0.0005 mol %, or at least 0.001 mol %, or at least 0.002 mol %, or at least 0.005 mol %, or at least 0.01 mol %, or at least 0.02 mol %, or at least 0.05 mol % based on the total molar amount of the terminal alkene.
- the ruthenium catalyst is a ruthenium complex and the amount of the ruthenium catalyst is no more than 0.2 mol %, or no more than 0.15 mol %, or no more than 0.1 mol % based on the total molar amount of the terminal alkene.
- the amount of the ruthenium complex is from about 0.0001 mol % to about 0.2 mol %, or from about 0.001 mol % to about 0.2 mol %, or from about 0.005 mol % to about 0.2 mol %, or from about 0.01 mol % to about 0.15 mol %, or from about 0.05 mol % to about 0.1 mol % based on the total molar amount of the terminal alkene.
- the ruthenium catalyst is a ruthenium salt and the amount of the ruthenium catalyst is at least 0.01 mol %, or at least 0.02 mol %, or at least 0.05 mol % based on the total molar amount of the terminal alkene. In some embodiments, the ruthenium catalyst is a ruthenium salt and the amount of the ruthenium catalyst is no more than 1 mol %, or no more than 0.8 mol %, or no more than 0.5 mol %, or no more than 0.4 mol %, or no more than 0.3 mol %, or no more than 0.2 mol % based on the total molar amount of the terminal alkene.
- the amount of the ruthenium salt is from about 0.01 mol % to about 1 mol %, or from about 0.01 mol % to about 0.5 mol %, or from about 0.02 mol % to about 0.3 mol %, or from about 0.05 mol % to about 0.2 mol % based on the total molar amount of the terminal alkene.
- the ruthenium catalyst comprises ruthenium or ruthenium compound supported on a catalyst support or carrier, that is, the ruthenium catalyst is a supported ruthenium catalyst.
- the catalyst support is selected from the group consisting of silica, alumina, carbon (e.g., activated carbon), TiO 2 , zeolite, and mixtures thereof. In some embodiments, the catalyst support is activated to provide more surface area.
- the catalyst support can be in any convenient form including particles, powders, granules, fibers, or shaped pieces.
- Ruthenium supported on the catalyst support can be in a cationic form (e.g., Ru +2 , Ru +3 ) or in a metal form.
- the ruthenium catalyst comprises RuCl 3 supported on a catalyst support.
- the ruthenium catalyst comprises ruthenium nanoparticles supported on a catalyst support.
- the supported ruthenium catalyst can be made by means known in the art including precipitation, coprecipitation, impregnation and methods of deposition or combination known in the art.
- the amount of ruthenium supported on a catalyst support is at least 0.01 wt %, or at least 0.02 wt %, or at least 0.05 wt %, or at least 0.1 wt %, or at least 0.2 wt %, or at least 0.5 wt %, or at least 1 wt % based on the total weight of the supported ruthenium catalyst.
- the amount of ruthenium supported on a catalyst support is no more than 30 wt %, or no more than 25 wt %, or no more than 20 wt %, or no more than 15 wt %, or no more than 10 wt %, or no more than 5 wt % based on the total weight of the supported ruthenium catalyst.
- the amount of ruthenium (supported on a catalyst support) means the amount of ruthenium element.
- the ruthenium catalyst comprises ruthenium or ruthenium compound supported on a catalyst support and the amount of ruthenium (supported on the catalyst support) is at least 0.0001 mol %, or at least 0.0002 mol %, or at least 0.0005 mol %, or at least 0.001 mol %, or at least 0.002 mol %, or at least 0.005 mol %, or at least 0.01 mol % comparing with the total molar amount of the terminal alkene.
- the ruthenium catalyst comprises ruthenium or ruthenium compound supported on a catalyst support and the amount of ruthenium (supported on the catalyst support) is no more than 1 mol %, or no more than 0.5 mol %, or no more than 0.2 mol %, or no more than 0.1 mol % comparing with the total molar amount of the terminal alkene.
- the isomerizing process is conducted at a temperature of at least about 120° C., or at least about 130° C., or at least about 140° C. In some embodiments, the isomerizing process is conducted at a temperature of no more than about 250° C., or no more than about 240° C., or no more than about 230° C., or no more than about 220° C., or no more than about 210° C., or no more than about 200° C. In some embodiments, the temperature is in a range of from about 120° C. to about 250° C., or from about 120° C. to about 240° C., or from about 120° C. to about 220° C., or from about 120° C.
- the isomerizing process in this disclosure can be carried out under atmospheric pressure or under pressures less than or greater than atmospheric pressure.
- the process may be carried out at a pressure ranging from about 30 millibar to about 5 bar.
- the isomerizing process is carried out under atmospheric pressure.
- the isomerizing process in this disclosure can be conducted under ambient atmosphere (i.e., air) or inert atmosphere.
- the isomerizing process is conducted under inert atmosphere such as under an inert gas atmosphere.
- inert gases include nitrogen and noble gases such as argon.
- the isomerizing process is conducted under a nitrogen gas atmosphere. In practice, the inert atmosphere may still contain minor amounts of oxygen.
- the isomerizing process is conducted under an inert gas atmosphere and under a pressure greater than atmospheric pressure. In some embodiments, the isomerizing process is conducted under ambient atmosphere.
- the isomerizing process time or isomerization reaction time is at least 10 minutes, or at least 20 minutes, or at least 0.5 hour, or at least 1 hour, or at least 1.5 hours, or at least 2 hours. In some embodiments, the isomerizing process time or isomerization reaction time is no more than 72 hours, or no more than 50 hours, or no more than 30 hours, or no more than 20 hours, or no more than 15 hours, or no more than 10 hours, or no more than 8 hours. In some embodiments, the isomerizing process time or isomerization reaction time is in a range of from about 0.5 to about 72 hours, or in a range of from about 1 to about 30 hours, or in a range of from about 2 to about 10 hours.
- the isomerizing process is conducted in the presence of a solvent.
- a solvent include alcohols, ethers, pentane, hexane, methylene chloride, chloroform and ethyl acetate.
- alcohol include methanol, ethanol, 1-propanol, isopropanol, butanol and its isomers, and pentanol and its isomers.
- alcohol is a tertiary alcohol such as tert-amyl alcohol.
- the amount of the solvent present in the reaction zone during the reaction is no more than 50 wt %, or no more than 40 wt %, or no more than 30 wt %, or no more than 20 wt %, or no more than 10 wt %, or no more than 5 wt %, or no more than 2 wt %, or no more than 1 wt %, or no more than 0.5 wt % based on the total weight of the terminal alkene.
- the reaction zone is substantially free or free of a solvent, that is, the isomerizing process is conducted essentially in the absence of or in the absence of a solvent.
- the reaction zone is substantially free or free of an additive, that is, the isomerizing process is conducted essentially in the absence of or in the absence of an additive.
- Typical additives include bases (organic bases or inorganic bases) such as amines and other nitrogen-containing organic bases, acetates, hydroxides and tert-butoxides, and co-catalysts such as strong Lewis acids (e.g., BF 3 ) and strong Bronsted acids (e.g., triflic acid).
- the total amount of the additives present in the reaction zone during the reaction is no more than 0.1 wt %, or no more than 0.05 wt %, or no more than 0.01 wt %, or no more than 0.005 wt %, or no more than 0.001 wt %, or no more than 0.0005 wt %, or no more than 0.0001 wt % based on the total weight of the terminal alkene.
- the reaction zone is substantially free or free of an additional ligand, that is, the isomerizing process is conducted essentially in the absence of or in the absence of an additional ligand.
- additional ligand means a ligand which is not present in the ruthenium complex used for the reaction.
- Typical additional ligands include carbon monoxide, carbene, phosphine and alkene-based compounds.
- the total amount of the additional ligands present in the reaction zone during the reaction is no more than 0.1 wt %, or no more than 0.05 wt %, or no more than 0.01 wt %, or no more than 0.005 wt %, or no more than 0.001 wt %, or no more than 0.0005 wt %, or no more than 0.0001 wt % based on the total weight of the terminal alkene.
- essentially no additional ligand is fed into the reaction zone before or during the reaction.
- the reaction zone is substantially free or free of an acid, that is, the isomerizing process is conducted essentially in the absence of or in the absence of an acid.
- Typical acids include triflic acid, HBF4 and sulfuric acid.
- the total amount of the acids present in the reaction zone during the reaction is no more than 0.1 wt %, or no more than 0.05 wt %, or no more than 0.01 wt %, or no more than 0.005 wt %, or no more than 0.001 wt %, or no more than 0.0005 wt %, or no more than 0.0001 wt % based on the total weight of the terminal alkene.
- the process in this disclosure comprises feeding a terminal alkene and a ruthenium catalyst into a reaction zone, and isomerizing the terminal alkene to form a product comprising an internal alkene in the presence of the ruthenium catalyst at a temperature of at least about 120° C., wherein the terminal alkene and the ruthenium catalyst are sole chemical reagents fed into the reaction zone before and during the isomerization reaction, that is, no chemical reagents other than the terminal alkene and the ruthenium catalyst is fed into the reaction zone before and during the isomerization reaction.
- the terminal alkene and the ruthenium catalyst may comprise impurities respectively.
- One advantage of the process in this disclosure is that it generates little or no HCl.
- a chlorine-containing ruthenium catalyst such as RuCl 3
- a small amount of HCl may be generated.
- no more than 3 mol %, or no more than 2 mol %, or no more than 1 mol %, or no more than 0.5 mol %, or no more than 0.1 mol %, or no more than 0.05 mol %, or no more than 0.01 mol %, or no more than 0.005 mol %, or no more than 0.001 mol % of HCl is generated based on the total molar amount of the terminal alkene.
- essentially no or no HCl is generated during the process.
- the terminal alkene is isomerized to form the internal alkene. It has been found that a double bond can migrate along a linear (unbranched) hydrocarbon chain during the process of this disclosure as shown in Scheme 1.
- the internal alkene product comprises an organic moiety represented by Formula II set forth below, that is, the double bond only migrates internally one position.
- the internal alkene product comprises an organic moiety represented by Formula IV or Formula V set forth below, that is, the double bond migrates internally one or more positions.
- the isomerization reaction in this disclosure has high conversion, selectivity and yield.
- the yield of the internal alkene i.e., isomerization reaction yield
- the yield of the internal alkene is at least 70%, or at least 80%, or at least 85%, or at least 90%, or at least 95%.
- the yield of the internal alkene is up to 98%, or up to 98.5%, or up to 99%, or up to 99.5%, or up to 100%.
- the yield of the internal alkene is in a range of from 70% to 100%, or in a range of from 90% to 99%, or in a range of from 95% to 98.5%.
- the process of this disclosure also comprises recovering the internal alkene.
- the internal alkene product can be recovered using procedures well known to the art.
- the internal alkene is recovered by distillation (e.g., fractional distillation).
- the internal alkene product can be used as fragrance ingredients or intermediates for the synthesis of fragrance ingredients.
- the terminal alkene starting material is a mixture of 2-propoxy-5-vinylcyclohexan-1-ol and 2-propoxy-4-vinylcyclohexan-1-ol
- the internal alkene product is a mixture of 2-propoxy-5-ethylidenecyclohexan-1-ol and 2-propoxy-4-ethylidenecyclohexan-1-ol.
- the ruthenium catalyst is a ruthenium complex and the amount of the ruthenium catalyst is at least 0.001 mol %, or at least 0.002 mol %, or at least 0.005 mol %, or at least 0.01 mol %, or at least 0.02 mol % based on the total molar amount of the terminal alkene.
- the ruthenium catalyst is a ruthenium complex and the amount of the ruthenium catalyst is no more than 0.2 mol %, or no more than 0.15 mol %, or no more than 0.1 mol % based on the total molar amount of the terminal alkene. In some embodiments, the amount of the ruthenium complex is from about 0.001 mol % to about 0.2 mol %, or from about 0.005 mol % to about 0.15 mol %, or from about 0.01 mol % to about 0.1 mol % based on the total molar amount of the terminal alkene.
- the terminal alkene starting material is methyl eugenol (1,2-dimethoxy-4-(prop-2-en-1-yl)benzene) and the internal alkene product is methyl isoeugenol (1,2-dimethoxy-4-(prop-1-en-1-yl)benzene).
- methyl isoeugenol includes both cis and trans isomers.
- the ruthenium catalyst is a ruthenium complex and the amount of the ruthenium catalyst is at least 0.0001 mol %, or at least 0.0002 mol %, or at least 0.0005 mol %, or at least 0.001 mol % based on the total molar amount of the terminal alkene. In some embodiments, the ruthenium catalyst is a ruthenium complex and the amount of the ruthenium catalyst is no more than 0.2 mol %, or no more than 0.15 mol %, or no more than 0.1 mol %, or no more than 0.05 mol %, or no more than 0.01 mol % based on the total molar amount of the terminal alkene.
- the amount of the ruthenium complex is from about 0.0001 mol % to about 0.05 mol %, or from about 0.0005 mol % to about 0.01 mol % based on the total molar amount of the terminal alkene.
- the terminal alkene starting material is 9-decen-1-ol and the internal alkene product comprises a mixture of 6-decen-1-ol, 7-decen-1-ol and 8-decen-1-ol.
- the internal alkene product further comprises other position isomers such as 5-decen-1-ol and 4-decen-1-ol.
- the ruthenium catalyst is a ruthenium complex and the amount of the ruthenium catalyst is at least 0.001 mol %, or at least 0.002 mol %, or at least 0.005 mol %, or at least 0.01 mol %, or at least 0.02 mol % based on the total molar amount of the terminal alkene. In some embodiments, the ruthenium catalyst is a ruthenium complex and the amount of the ruthenium catalyst is no more than 0.2 mol %, or no more than 0.15 mol %, or no more than 0.1 mol % based on the total molar amount of the terminal alkene.
- the amount of the ruthenium complex is from about 0.001 mol % to about 0.2 mol %, or from about 0.005 mol % to about 0.15 mol %, or from about 0.01 mol % to about 0.1 mol % based on the total molar amount of the terminal alkene.
- the isomerization reactions were carried out with the terminal alkene starting material and the ruthenium catalyst alone, that is, the isomerization reactions were carried out essentially free of a solvent, an additive, an acid, and an additional ligand.
- This example demonstrated that Veraspice fragrance ingredients 2a and 2b can be efficiently made with high yield by using Ru(methylallyl) 2 (COD) as the catalyst at very low concentration in the absence of a solvent.
- Example 2 Same process as Example 1 was conducted in Example 2 except that RuCl 2 (PPh 3 ) 3 was used as the catalyst for Example 2.
- the reaction temperature is also 150° C. Results are shown in Table 2.
- the isomerization reactions were carried out with the terminal alkene starting material and the ruthenium catalyst alone, that is, the isomerization reactions were carried out essentially free of a solvent, an additive, an acid, and an additional ligand.
- This example demonstrated that Veraspice fragrance ingredients 2a and 2b can be efficiently made with high yield by using RuCl 2 (PPh 3 ) 3 as the catalyst at very low concentration in the absence of a solvent.
- Example 3 Same process as Example 1 was conducted in Example 3 except that RuCl 3 was used as the catalyst for Example 3. The reaction temperature is also 150° C. Results are shown in Table 3.
- the isomerization reactions were carried out with the terminal alkene starting material and the ruthenium catalyst alone, that is, the isomerization reactions were carried out essentially free of a solvent, an additive, an acid, and an additional ligand.
- This example demonstrated that Veraspice fragrance ingredients 2a and 2b can be efficiently made with high yield by using RuCl 3 as the catalyst at low concentration in the absence of a solvent.
- Methyl eugenol (1 mL) was charged into a 2 mL or 8 mL vial equipped with a magnetic stirrer and the Ru(methylallyl) 2 (COD) catalyst (0.0001-5 mol %) was added.
- the vial was closed with a cap, placed in a pre-heated bath oil at the reaction temperature of 150° C. under magnetically stirring and maintained during the reaction time.
- the product mixture comprising methyl isoeugenol was characterised by GC and NMR. Results are shown in Table 4.
- the isomerization reactions were carried out with the terminal alkene starting material and the ruthenium catalyst alone, that is, the isomerization reactions were carried out essentially free of a solvent, an additive, an acid, and an additional ligand.
- This example demonstrated that methyl isoeugenol can be efficiently made with high yield by using Ru(methylallyl) 2 (COD) as the catalyst at very low concentration in the absence of a solvent.
- Methyl eugenol (1 mL) was charged into a 2 mL or 8 mL vial equipped with a magnetic stirrer and a catalyst (0.01 mol %) was added. The vial was closed with a cap, placed in a pre-heated bath oil at the reaction temperature of 150° C. under magnetically stirring and maintained for one hour (reaction time). After one hour reaction time, the reaction was stopped and cooled. The product mixture was characterised by GC and NMR for the cis and trans methyl isoeugenol content. Results are shown in Table 5.
- Fe(CO) 5 dis means Fe(CO) 5 previously dissolved in methyl eugenol before adding to the vial. In this experiment, the total amount of methyl eugenol fed to the vial was still 1 mL.
- the isomerization reactions were carried out with the terminal alkene starting material and the catalyst alone, that is, the isomerization reactions were carried out essentially free of a solvent, an additive, an acid, and an additional ligand.
- This example demonstrated that while the ruthenium catalyst got nearly quantitatively the isomerized product in just one hour reaction time, with very high selectivity and without branched nor oligomerized products, other metal catalysts were barely active under solvent- and additive-free reaction conditons.
- Methyl eugenol (1 mL) was charged into a 2 mL or 8 mL vial equipped with a magnetic stirrer and a ruthenium catalyst (0.001 mol %) was added. The vial was closed with a cap, placed in a pre-heated bath oil at the reaction temperature of 150° C. under magnetically stirring and maintained for four hours (reaction time). After four hours reaction time, the reaction was stopped and cooled. The product mixture comprising methyl isoeugenol was characterised by GC and NMR. Results are shown in Table 6.
- the isomerization reactions were carried out with the terminal alkene starting material and the ruthenium catalyst alone, that is, the isomerization reactions were carried out essentially free of a solvent, an additive, an acid, and an additional ligand.
- This example demonstrated that methyl isoeugenol can be efficiently made with high yield by using ruthenium complexes at 0.001 mol% (10 ppm) amount in the absence of a solvent.
- Methyl eugenol (1 mL) was charged into a 2 mL or 8 mL vial equipped with a magnetic stirrer and a ruthenium catalyst comprising ruthenium supported on a catalyst support (supported ruthenium catalyst) was added.
- the vial was closed with a cap, placed in a pre-heated bath oil at the reaction temperature of 150° C. under magnetically stirring and maintained during the reaction time.
- the supported ruthenium catalysts were either commercial or prepared by impregnation of aqueous RuCl 3 .
- the product mixture comprising methyl isoeugenol was characterised by GC and NMR. Results are shown in Table 7.
- wt % Ru means the amount of ruthenium supported on the catalyst support based on the total weight of the supported ruthenium catalyst
- mol % Ru means the amount of ruthenium supported on the catalyst support comparing with the total molar amount of the terminal alkene
- KY means zeolite Y with potassium.
- the isomerization reactions were carried out with the terminal alkene starting material and the supported ruthenium catalyst alone, that is, the isomerization reactions were carried out essentially free of a solvent, an additive, an acid, and an additional ligand.
- This example demonstrated that methyl isoeugenol can be efficiently made with high yield by using supported ruthenium catalysts at very low ruthenium concentration in the absence of a solvent.
- 9-decen-1-ol (1 mL) was charged into a 2 mL or 8 mL vial equipped with a magnetic stirrer and the Ru(methylallyl) 2 (COD) catalyst (0.0001-0.1 mol %) was added.
- the vial was closed with a cap, placed in a pre-heated bath oil at the reaction temperature of 150° C. under magnetically stirring and maintained during the reaction time.
- the product mixture comprising isomers x-decen-1-ol (x is an integer from 2 to 8) was characterised by GC and NMR. Results are shown in Table 8.
- Cat. (mol %) means the amount of Ru(methylallyl) 2 (COD) catalyst in mol % based on the total molar amount of the terminal alkene
- T (h) means reaction time in hours.
- the isomerization reactions were carried out with the terminal alkene starting material and the ruthenium catalyst alone, that is, the isomerization reactions were carried out essentially free of a solvent, an additive, an acid, and an additional ligand.
- This example demonstrated that isorosalva fragrance intermediates can be efficiently made with high yield by using Ru(methylallyl) 2 (COD) as the catalyst at very low concentration in the absence of a solvent.
- Example 9 Same process as Example 8 was conducted in Example 9 except that the reaction temperature is 175° C. in this Example. Results are shown in Table 9.
- Example 10 Same process as Example 8 was conducted in Example 10 except that the reaction temperature is 200° C. in this Example. Results are shown in Table 10.
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Abstract
This disclosure relates to a process for making fragrance ingredient or fragrance intermediate which involves isomerizing a starting material comprising a terminal alkene to form a product comprising an internal alkene in the presence of a ruthenium catalyst at a temperature of at least about 120° C.
Description
- The present disclosure relates to a selective alkene isomerization process to convert a terminal alkene to an internal alkene by using a ruthenium catalyst and more particularly to a process for making fragrance ingredient or fragrance intermediate.
- Alkene isomerization reactions have been identified as one of the key transformations that affords either final fragrance ingredients or valuable synthetic intermediates. However, each of these processes require different catalyst and conditions. Furthermore, isomerizations need to provide maximum conversion and be highly selective. Structural differences among starting material, desired final product and isomeric byproducts are in certain cases minimal, making final purification and/or isolation challenging due to the very similar physicochemical properties.
- The isomerization of alkenes allows to move the double bond within a molecule to the desired position with full atom economy. However, the reported metal catalysts for this reaction are generally very expensive and give unacceptable mixture of alkene products (for representative examples see: Science 2019, 363, 391-396; ChemCatChem 2017, 9, 3849-3859; M. Mayer, A. Welther, A. J. von Wangelin,
ChemCatChem 2011, 3, 1567-1571; R. Uma, C. Crévisy, R. Grée, Chem. Rev. 2003, 103, 27-51; Y. Sasson, A. Zoran, J. Blum, J. Mol. Cat. 1981, 11, 293-300). In general, homogeneous Lewis acid catalysts are commonly employed in the Fine Chemical Industry for double bond isomerization reactions. Alternative catalysts include solid acid catalysts containing Brönsted, Lewis or both type of acid centers (for selected examples see: J. Catal. 1962, 1, 2231; EP211985A1; EP442159B1; US20150141720A1) such as sulfated-zirconias, metal (usually Pt) supported zeolites heteropolyacids, molybdenum oxides, Al2O3-TiO2 and alkali exchanged (X type) or alumina doped (K, Na, Cs . . .) zeolites (see, for instance, U.S. Pat. No. 4,992,613A; Catal. Surv. Japan, 2002, 5, 81; WO9313038). However, these types of acid solids, nowadays widely used for skeletal isomerization in the petrochemical industry at high temperatures of 250-450° C. (see for instance: Ind. Eng. Chem., 1953, 45, 551-564; Synthesis, 1969, 97-112; Synth. Commun., 1997, 27, 4335-4340), are usually unsuitable for fine chemical products. - The present disclosure provides an isomerization process for making fragrance ingredient or fragrance intermediate. The process converts a terminal alkene to an internal alkene and comprises isomerizing a starting material comprising a terminal alkene to form a product comprising an internal alkene in the presence of a ruthenium catalyst at a temperature of at least about 120° C. in a reaction zone.
- Embodiments are illustrated in the accompanying figures to improve understanding of concepts as presented herein.
-
FIG. 1 shows molecular structures of some ruthenium complexes. - The foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as defined in the appended claims. Other features and benefits of any one or more of the embodiments will be apparent from the following detailed description, and from the claims.
- As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Further, unless expressly stated to the contrary, “or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
- Also, use of “a” or “an” are employed to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.
- Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the present invention, suitable methods and materials are described below. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.
- When an amount, concentration, or other value or parameter is given as either a range, preferred range or a list of upper preferable values and/or lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range. For example, when a range of “1 to 10” is recited, the recited range should be construed as including ranges “1 to 8”, “3 to 10”, “2 to 7”, “1.5 to 6”, “3.4 to 7.8”, “1 to 2 and 7-10”, “2 to 4 and 6 to 9”, “1 to 3.6 and 7.2 to 8.9”, “1-5 and 10”, “2 and 8 to 10”, “1.5-4 and 8”, and the like.
- While compositions and methods are described herein in terms of “comprising” various components or steps, the compositions and methods also can “consist essentially of” or “consist of” the various components or steps, unless stated otherwise.
- Some alkene molecules may exist as cis or trans stereoisomers. Unless explicitly indicated, an alkene (molecule, structure, formula, or chemical name) as used herein includes both cis and trans stereoisomers, as well as any combinations or mixtures of the cis and trans stereoisomers.
- Before addressing details of embodiments described below, some terms are defined or clarified.
- The term “terminal alkene”, as used herein, means a molecule comprising an organic moiety represented by Formula I set forth below:
- In a terminal alkene, the double bond is on a terminal carbon.
- The term “internal alkene”, as used herein, means a molecule comprising a double bond which is not on the terminal carbon. In some embodiments, the internal alkene means a molecule comprising an organic moiety represented by Formula II set forth below:
- In some embodiments, the terminal alkene is a molecule comprising an organic moiety represented by Formula III set forth below wherein n is an integer from 1 to 20:
- In such embodiments, the internal alkene is a molecule comprising an organic moiety represented by Formula IV, or a molecule comprising an organic moiety represented by Formula V, or mixtures of molecules of Formula IV and Formula V, as shown below:
- wherein l and m independently is an integer of 0 or greater than 0 (positive integer), and l+m=n−1. In some embodiments, n is an integer from 1 to 15, or an integer from 1 to 10. In some embodiments, n is 1.
- Terminal alkene in this disclosure is a primary alkene, that is, the double bond is only connected to one carbon. The term “secondary alkene”, as used herein, means a molecule comprising a double bond which is connected to two carbons. The term “tertiary alkene”, as used herein, means a molecule comprising a double bond which is connected to three carbons. The term “quaternary alkene”, as used herein, means a molecule comprising a double bond which is connected to four carbons. A double bond in an aromatic functional group is not deemed as the kind of double bond referred to above in the definition of the terms secondary alkene, tertiary alkene and quaternary alkene.
- The term “ruthenium complex”, as used herein, means a ruthenium coordination complex comprising a central ruthenium atom or cation surrounded by one or more coordination ligands that bind to the central ruthenium atom or cation. The bonding with the ruthenium atom or cation generally involves formal donation of one or more of the ligand's electron pairs.
- The term “yield of the internal alkene”, as used herein, means the total molar amount of the internal alkene (product) formed in the isomerizing process (reaction) comparing with the total molar amount of the terminal alkene (starting material).
- The term “fragrance intermediate”, as used herein, means an intermediate molecule (e.g., formed during multiple-step chemical reactions) which can react or be transformed to provide a final molecule which can be used as a fragrance ingredient.
- In the process of this disclosure, a terminal alkene starting material is converted by an isomerization reaction to an internal alkene product. The terminal alkene starting material and the internal alkene product are position isomers, that is, they are different only on the position of the double bond. The isomerization process can be conducted by contacting a starting material comprising a terminal alkene with a ruthenium catalyst in a reaction zone. In some embodiments, the starting material comprises at least 80 wt %, or at least 85 wt %, or at least 90 wt %, or at least 95 wt %, or at least 98 wt %, or at least 99 wt % of the terminal alkene based on the total weight of the starting material. In some embodiments, the starting material consists essentially of or consists of the terminal alkene.
- In some embodiments, the starting material comprises no more than 10 mol %, or no more than 5 mol %, or no more than 2 mol %, or no more than 1 mol %, or no more than 0.5 mol %, or no more than 0.2 mol %, or no more than 0.1 mol %, or no more than 0.05 mol %, or no more than 0.02 mol %, or no more than 0.01 mol % of a secondary alkene based on the total molar amount of the starting material. In some embodiments, the starting material is substantially free or free of a secondary alkene.
- In some embodiments, the starting material comprises no more than 10 mol %, or no more than 5 mol %, or no more than 2 mol %, or no more than 1 mol %, or no more than 0.5 mol %, or no more than 0.2 mol %, or no more than 0.1 mol %, or no more than 0.05 mol %, or no more than 0.02 mol %, or no more than 0.01 mol % of a tertiary alkene based on the total molar amount of the starting material. In some embodiments, the starting material is substantially free or free of a tertiary alkene.
- In some embodiments, the starting material comprises no more than 10 mol %, or no more than 5 mol %, or no more than 2 mol %, or no more than 1 mol %, or no more than 0.5 mol %, or no more than 0.2 mol %, or no more than 0.1 mol %, or no more than 0.05 mol %, or no more than 0.02 mol %, or no more than 0.01 mol % of a quaternary alkene based on the total molar amount of the starting material. In some embodiments, the starting material is substantially free or free of a quaternary alkene.
- The terminal alkene molecule can comprise one or more functional groups containing oxygen and/or halide atoms. In some embodiments, the terminal alkene molecule comprises one or more functional groups selected from the group consisting of alkyl, aryl, alkoxy, hydroxy, halide and ester. In some embodiments, the terminal alkene molecule comprises one or more functional groups selected from the group consisting of alkyl, aryl, alkoxy and hydroxy.
- In some embodiments, the terminal alkene molecule does not comprise nitrogen element. In some embodiments, the terminal alkene molecule does not comprise an organic basic group. In some embodiments, the terminal alkene molecule does not comprise an amine functional group.
- In the process of this disclosure, a starting material comprising a terminal alkene is isomerized to form a product comprising an internal alkene in the presence of a ruthenium catalyst. The ruthenium catalyst is a ruthenium-containing catalyst which catalyzes the positional isomerization of the terminal alkene. Unless explicitly indicated, the ruthenium catalyst is not supported on a catalyst support or carrier. In some embodiments, the ruthenium catalyst is selected from the group consisting of ruthenium complexes, ruthenium salts, ruthenium in metal form, and mixtures thereof. In some embodiments, the ruthenium complexe is selected from the group consisting of ruthenium alkene complexes, ruthenium carbonyl complexes, ruthenium phosphine complexes, and mixtures thereof. In some embodiments, the ruthenium salt is selected from the group consisting of ruthenium chlorides, ruthenium bromides, ruthenium iodides, ruthenium oxides, ruthenium triflates, ruthenium perchlorates, and mixtures thereof. Ruthenium salts can be in anhydrous or hydrated form. Examples of ruthenium in metal form include ruthenium black.
- In some embodiments, ruthenium is in an oxidation state of 0, II or III in a ruthenium catalyst. In some embodiments, the ruthenium catalyst comprises no more than 20 wt %, or no more than 15 wt %, or no more than 10 wt %, or no more than 5 wt %, or no more than 1 wt %, or no more than 0.2 wt %, or no more than 0.1 wt %, or no more than 0.05 wt %, or no more than 0.02 wt %, or no more than 0.01 wt % of a ruthenium compound having oxidation state of IV or higher based on the total weight of the ruthenium catalyst. In some embodiments, the ruthenium catalyst is substantially free or free of a ruthenium compound having oxidation state of IV or higher.
- In some embodiments, the ruthenium complex is selected from the group consisting of bis(2-methylallyl)(1,5-cyclooctadiene)ruthenium(II) complex (Ru(methylallyl)2(COD)), dichlorotris(triphenylphosphine)ruthenium(II) complex (RuCl2(PPh3)3), dichlorobis(2-(diphenylphosphino)ethylamine)ruthenium(II) complex (RuCl2(C14H16NP)2), carbonyldihydridotris(triphenylphosphine)ruthenium(II) complex (Ru(CO)H2(PPh3)3), triruthenium dodecacarbonyl complex (Ru3(CO)12), dichloro(benzylidene)bis(tricyclohexylphosphine)ruthenium(II) complex (Grubbs 1st generation), dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](benzylidene) (tricyclohexylphosphine)ruthenium(II) complex (Grubbs 2nd generation), dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](2-isopropoxyphenylmethylene)ruthenium(II) complex (Hoveyda-Grubbs 2nd generation), [2-(di-tert-butylphosphinomethyl)-6-(diethylaminomethyl)pyridine]carbonylchlorohydridoruthenium(II) complex (C20H36CIN2OPRu, Milstein), dichlorotriphenylphosphine[2-(diphenylphosphino)-N-(2 pyridinylmethyl)ethanamine]ruthenium(II) complex (C38H36Cl2N2P2Ru, Gusev Ru-PNN), and mixtures thereof. Molecular structures of some ruthenium complexes are shown in
FIG. 1 . - In some embodiments, the ruthenium complex is selected from the group consisting of bis(2-methylallyl)(1,5-cyclooctadiene)ruthenium(II) complex (Ru(methylallyl)2(COD)), dichlorotris(triphenylphosphine)ruthenium(II) complex (RuCl2(PPh3)3), and mixtures thereof. In some embodiments, the ruthenium complex is dichlorotris(triphenylphosphine)ruthenium(II) complex.
- In some embodiments, the ruthenium complex is fully dissolved in the terminal alkene starting material under the process or reaction conditions in this disclosure. In some embodiments, at least 70 wt %, or at least 80 wt %, or at least 85 wt %, or at least 90 wt %, or at least 95 wt %, or at least 98 wt % of the ruthenium complex used in the process (based on the total weight of the ruthenium complex used in the process) is dissolved in the terminal alkene starting material under the process or reaction conditions.
- In some embodiments, the ruthenium salt is RuCl3 (anhydrous and/or hydrated). In some embodiments, the ruthenium salt is essentially insoluble in the terminal alkene starting material under the process or reaction conditions in this disclosure. In some embodiments, the solubility of the ruthenium salt is no more than 30 wt %, or no more than 20 wt %, or no more than 15 wt %, or no more than 10 wt %, or no more than 5 wt %, or no more than 2 wt %, or no more than 1 wt %, or no more than 0.5 wt %, or no more than 0.2 wt %, or no more than 0.1 wt %, or no more than 0.05 wt %, or no more than 0.02 wt %, or no more than 0.01 wt % (based on the total weight of the ruthenium salt used in the process) in the terminal alkene starting material under the process or reaction conditions.
- In some embodiments, the amount of the ruthenium catalyst is at least 0.0001 mol %, or at least 0.0002 mol %, or at least 0.0005 mol %, or at least 0.001 mol %, or at least 0.002 mol %, or at least 0.005 mol %, or at least 0.01 mol %, or at least 0.02 mol %, or at least 0.05 mol % based on the total molar amount of the terminal alkene. In some embodiments, the amount of the ruthenium catalyst is no more than 1 mol %, or no more than 0.8 mol %, or no more than 0.5 mol %, or no more than 0.4 mol %, or no more than 0.3 mol %, or no more than 0.2 mol %, or no more than 0.15 mol %, or no more than 0.1 mol % based on the total molar amount of the terminal alkene.
- In some embodiments, the ruthenium catalyst is a ruthenium complex and the amount of the ruthenium catalyst is at least 0.0001 mol %, or at least 0.0002 mol %, or at least 0.0005 mol %, or at least 0.001 mol %, or at least 0.002 mol %, or at least 0.005 mol %, or at least 0.01 mol %, or at least 0.02 mol %, or at least 0.05 mol % based on the total molar amount of the terminal alkene. In some embodiments, the ruthenium catalyst is a ruthenium complex and the amount of the ruthenium catalyst is no more than 0.2 mol %, or no more than 0.15 mol %, or no more than 0.1 mol % based on the total molar amount of the terminal alkene. In some embodiments, the amount of the ruthenium complex is from about 0.0001 mol % to about 0.2 mol %, or from about 0.001 mol % to about 0.2 mol %, or from about 0.005 mol % to about 0.2 mol %, or from about 0.01 mol % to about 0.15 mol %, or from about 0.05 mol % to about 0.1 mol % based on the total molar amount of the terminal alkene.
- In some embodiments, the ruthenium catalyst is a ruthenium salt and the amount of the ruthenium catalyst is at least 0.01 mol %, or at least 0.02 mol %, or at least 0.05 mol % based on the total molar amount of the terminal alkene. In some embodiments, the ruthenium catalyst is a ruthenium salt and the amount of the ruthenium catalyst is no more than 1 mol %, or no more than 0.8 mol %, or no more than 0.5 mol %, or no more than 0.4 mol %, or no more than 0.3 mol %, or no more than 0.2 mol % based on the total molar amount of the terminal alkene. In some embodiments, the amount of the ruthenium salt is from about 0.01 mol % to about 1 mol %, or from about 0.01 mol % to about 0.5 mol %, or from about 0.02 mol % to about 0.3 mol %, or from about 0.05 mol % to about 0.2 mol % based on the total molar amount of the terminal alkene.
- In some embodiments, the ruthenium catalyst comprises ruthenium or ruthenium compound supported on a catalyst support or carrier, that is, the ruthenium catalyst is a supported ruthenium catalyst. In some embodiments, the catalyst support is selected from the group consisting of silica, alumina, carbon (e.g., activated carbon), TiO2, zeolite, and mixtures thereof. In some embodiments, the catalyst support is activated to provide more surface area. The catalyst support can be in any convenient form including particles, powders, granules, fibers, or shaped pieces.
- Ruthenium supported on the catalyst support can be in a cationic form (e.g., Ru+2, Ru+3) or in a metal form. In some embodiments, the ruthenium catalyst comprises RuCl3 supported on a catalyst support. In some embodiments, the ruthenium catalyst comprises ruthenium nanoparticles supported on a catalyst support. The supported ruthenium catalyst can be made by means known in the art including precipitation, coprecipitation, impregnation and methods of deposition or combination known in the art.
- In some embodiments, the amount of ruthenium supported on a catalyst support is at least 0.01 wt %, or at least 0.02 wt %, or at least 0.05 wt %, or at least 0.1 wt %, or at least 0.2 wt %, or at least 0.5 wt %, or at least 1 wt % based on the total weight of the supported ruthenium catalyst. In some embodiments, the amount of ruthenium supported on a catalyst support is no more than 30 wt %, or no more than 25 wt %, or no more than 20 wt %, or no more than 15 wt %, or no more than 10 wt %, or no more than 5 wt % based on the total weight of the supported ruthenium catalyst. In embodiments of the supported ruthenium catalyst, the amount of ruthenium (supported on a catalyst support) means the amount of ruthenium element.
- In some embodiments, the ruthenium catalyst comprises ruthenium or ruthenium compound supported on a catalyst support and the amount of ruthenium (supported on the catalyst support) is at least 0.0001 mol %, or at least 0.0002 mol %, or at least 0.0005 mol %, or at least 0.001 mol %, or at least 0.002 mol %, or at least 0.005 mol %, or at least 0.01 mol % comparing with the total molar amount of the terminal alkene. In some embodiments, the ruthenium catalyst comprises ruthenium or ruthenium compound supported on a catalyst support and the amount of ruthenium (supported on the catalyst support) is no more than 1 mol %, or no more than 0.5 mol %, or no more than 0.2 mol %, or no more than 0.1 mol % comparing with the total molar amount of the terminal alkene.
- In the process of this disclosure, the isomerizing process is conducted at a temperature of at least about 120° C., or at least about 130° C., or at least about 140° C. In some embodiments, the isomerizing process is conducted at a temperature of no more than about 250° C., or no more than about 240° C., or no more than about 230° C., or no more than about 220° C., or no more than about 210° C., or no more than about 200° C. In some embodiments, the temperature is in a range of from about 120° C. to about 250° C., or from about 120° C. to about 240° C., or from about 120° C. to about 220° C., or from about 120° C. to about 200° C., or from about 130° C. to about 250° C., or from about 130° C. to about 240° C., or from about 130° C. to about 220° C., or from about 140° C. to about 250° C., or from about 140° C. to about 220° C.
- The isomerizing process in this disclosure can be carried out under atmospheric pressure or under pressures less than or greater than atmospheric pressure. For example, the process may be carried out at a pressure ranging from about 30 millibar to about 5 bar. In some embodiments, the isomerizing process is carried out under atmospheric pressure.
- The isomerizing process in this disclosure can be conducted under ambient atmosphere (i.e., air) or inert atmosphere. In some embodiments, the isomerizing process is conducted under inert atmosphere such as under an inert gas atmosphere. Examples of inert gases include nitrogen and noble gases such as argon. In some embodiments, the isomerizing process is conducted under a nitrogen gas atmosphere. In practice, the inert atmosphere may still contain minor amounts of oxygen. In some embodiments, the isomerizing process is conducted under an inert gas atmosphere and under a pressure greater than atmospheric pressure. In some embodiments, the isomerizing process is conducted under ambient atmosphere.
- In some embodiments, the isomerizing process time or isomerization reaction time is at least 10 minutes, or at least 20 minutes, or at least 0.5 hour, or at least 1 hour, or at least 1.5 hours, or at least 2 hours. In some embodiments, the isomerizing process time or isomerization reaction time is no more than 72 hours, or no more than 50 hours, or no more than 30 hours, or no more than 20 hours, or no more than 15 hours, or no more than 10 hours, or no more than 8 hours. In some embodiments, the isomerizing process time or isomerization reaction time is in a range of from about 0.5 to about 72 hours, or in a range of from about 1 to about 30 hours, or in a range of from about 2 to about 10 hours.
- In some embodiments, the isomerizing process is conducted in the presence of a solvent. Examples of the solvent include alcohols, ethers, pentane, hexane, methylene chloride, chloroform and ethyl acetate. Examples of alcohol include methanol, ethanol, 1-propanol, isopropanol, butanol and its isomers, and pentanol and its isomers. In some embodiments, alcohol is a tertiary alcohol such as tert-amyl alcohol. In some embodiments, the amount of the solvent present in the reaction zone during the reaction is no more than 50 wt %, or no more than 40 wt %, or no more than 30 wt %, or no more than 20 wt %, or no more than 10 wt %, or no more than 5 wt %, or no more than 2 wt %, or no more than 1 wt %, or no more than 0.5 wt % based on the total weight of the terminal alkene. In some embodiments, the reaction zone is substantially free or free of a solvent, that is, the isomerizing process is conducted essentially in the absence of or in the absence of a solvent.
- In some embodiments, the reaction zone is substantially free or free of an additive, that is, the isomerizing process is conducted essentially in the absence of or in the absence of an additive. Typical additives include bases (organic bases or inorganic bases) such as amines and other nitrogen-containing organic bases, acetates, hydroxides and tert-butoxides, and co-catalysts such as strong Lewis acids (e.g., BF3) and strong Bronsted acids (e.g., triflic acid). In some embodiments, the total amount of the additives present in the reaction zone during the reaction is no more than 0.1 wt %, or no more than 0.05 wt %, or no more than 0.01 wt %, or no more than 0.005 wt %, or no more than 0.001 wt %, or no more than 0.0005 wt %, or no more than 0.0001 wt % based on the total weight of the terminal alkene.
- In some embodiments, the reaction zone is substantially free or free of an additional ligand, that is, the isomerizing process is conducted essentially in the absence of or in the absence of an additional ligand. By “additional ligand” means a ligand which is not present in the ruthenium complex used for the reaction. Typical additional ligands include carbon monoxide, carbene, phosphine and alkene-based compounds. In some embodiments, the total amount of the additional ligands present in the reaction zone during the reaction is no more than 0.1 wt %, or no more than 0.05 wt %, or no more than 0.01 wt %, or no more than 0.005 wt %, or no more than 0.001 wt %, or no more than 0.0005 wt %, or no more than 0.0001 wt % based on the total weight of the terminal alkene. In some embodiments, essentially no additional ligand is fed into the reaction zone before or during the reaction.
- In some embodiments, the reaction zone is substantially free or free of an acid, that is, the isomerizing process is conducted essentially in the absence of or in the absence of an acid. Typical acids include triflic acid, HBF4 and sulfuric acid. In some embodiments, the total amount of the acids present in the reaction zone during the reaction is no more than 0.1 wt %, or no more than 0.05 wt %, or no more than 0.01 wt %, or no more than 0.005 wt %, or no more than 0.001 wt %, or no more than 0.0005 wt %, or no more than 0.0001 wt % based on the total weight of the terminal alkene.
- In some embodiments, the process in this disclosure comprises feeding a terminal alkene and a ruthenium catalyst into a reaction zone, and isomerizing the terminal alkene to form a product comprising an internal alkene in the presence of the ruthenium catalyst at a temperature of at least about 120° C., wherein the terminal alkene and the ruthenium catalyst are sole chemical reagents fed into the reaction zone before and during the isomerization reaction, that is, no chemical reagents other than the terminal alkene and the ruthenium catalyst is fed into the reaction zone before and during the isomerization reaction. It is to be appreciated that the terminal alkene and the ruthenium catalyst may comprise impurities respectively.
- One advantage of the process in this disclosure is that it generates little or no HCl. When a chlorine-containing ruthenium catalyst such as RuCl3 is used in the process, a small amount of HCl may be generated. Typically during the process of this disclosure, no more than 3 mol %, or no more than 2 mol %, or no more than 1 mol %, or no more than 0.5 mol %, or no more than 0.1 mol %, or no more than 0.05 mol %, or no more than 0.01 mol %, or no more than 0.005 mol %, or no more than 0.001 mol % of HCl is generated based on the total molar amount of the terminal alkene. In some embodiments, essentially no or no HCl is generated during the process.
- During the process of this disclosure, the terminal alkene is isomerized to form the internal alkene. It has been found that a double bond can migrate along a linear (unbranched) hydrocarbon chain during the process of this disclosure as shown in Scheme 1.
- It has also been found that such double bond migration (along the hydrocarbon chain) stops at a branched carbon. It has further been found that the process of this disclosure does not work when a secondary alkene, a tertiary alkene, or a quaternary alkene is used as the starting material, that is, the process of this disclosure is selective for a primary alkene starting material.
- In some embodiments, the internal alkene product comprises an organic moiety represented by Formula II set forth below, that is, the double bond only migrates internally one position.
- In some embodiments, the internal alkene product comprises an organic moiety represented by Formula IV or Formula V set forth below, that is, the double bond migrates internally one or more positions.
- In Formulas IV and V, n is an integer from 1 to 20. In some embodiments, n is an integer from 1 to 15, or an integer from 1 to 10. In some embodiments, n is 1. Moreover, I and m independently is an integer of 0 or greater than 0 (positive integer), and I+m=n−1.
- The isomerization reaction in this disclosure has high conversion, selectivity and yield. In some embodiments, the yield of the internal alkene (i.e., isomerization reaction yield) is at least 70%, or at least 80%, or at least 85%, or at least 90%, or at least 95%. In some embodiments, the yield of the internal alkene is up to 98%, or up to 98.5%, or up to 99%, or up to 99.5%, or up to 100%. In some embodiments, the yield of the internal alkene is in a range of from 70% to 100%, or in a range of from 90% to 99%, or in a range of from 95% to 98.5%.
- In some embodiments, the process of this disclosure also comprises recovering the internal alkene. The internal alkene product can be recovered using procedures well known to the art. In some embodiments, the internal alkene is recovered by distillation (e.g., fractional distillation). In some embodiments, the internal alkene product can be used as fragrance ingredients or intermediates for the synthesis of fragrance ingredients.
- In some embodiments, the terminal alkene starting material is a mixture of 2-propoxy-5-vinylcyclohexan-1-ol and 2-propoxy-4-vinylcyclohexan-1-ol, and the internal alkene product is a mixture of 2-propoxy-5-ethylidenecyclohexan-1-ol and 2-propoxy-4-ethylidenecyclohexan-1-ol. During the isomerizing process, 2-propoxy-5-vinylcyclohexan-1-ol is converted to 2-propoxy-5-ethylidenecyclohexan-1-ol, and 2-propoxy-4-vinylcyclohexan-1-ol is converted to 2-propoxy-4-ethylidenecyclohexan-1-ol. In some embodiments, the ruthenium catalyst is a ruthenium complex and the amount of the ruthenium catalyst is at least 0.001 mol %, or at least 0.002 mol %, or at least 0.005 mol %, or at least 0.01 mol %, or at least 0.02 mol % based on the total molar amount of the terminal alkene. In some embodiments, the ruthenium catalyst is a ruthenium complex and the amount of the ruthenium catalyst is no more than 0.2 mol %, or no more than 0.15 mol %, or no more than 0.1 mol % based on the total molar amount of the terminal alkene. In some embodiments, the amount of the ruthenium complex is from about 0.001 mol % to about 0.2 mol %, or from about 0.005 mol % to about 0.15 mol %, or from about 0.01 mol % to about 0.1 mol % based on the total molar amount of the terminal alkene.
- In some embodiments, the terminal alkene starting material is methyl eugenol (1,2-dimethoxy-4-(prop-2-en-1-yl)benzene) and the internal alkene product is methyl isoeugenol (1,2-dimethoxy-4-(prop-1-en-1-yl)benzene). The term “methyl isoeugenol”, as used herein, includes both cis and trans isomers. In some embodiments, the ruthenium catalyst is a ruthenium complex and the amount of the ruthenium catalyst is at least 0.0001 mol %, or at least 0.0002 mol %, or at least 0.0005 mol %, or at least 0.001 mol % based on the total molar amount of the terminal alkene. In some embodiments, the ruthenium catalyst is a ruthenium complex and the amount of the ruthenium catalyst is no more than 0.2 mol %, or no more than 0.15 mol %, or no more than 0.1 mol %, or no more than 0.05 mol %, or no more than 0.01 mol % based on the total molar amount of the terminal alkene. In some embodiments, the amount of the ruthenium complex is from about 0.0001 mol % to about 0.05 mol %, or from about 0.0005 mol % to about 0.01 mol % based on the total molar amount of the terminal alkene.
- In some embodiments, the terminal alkene starting material is 9-decen-1-ol and the internal alkene product comprises a mixture of 6-decen-1-ol, 7-decen-1-ol and 8-decen-1-ol. In some embodiments, the internal alkene product further comprises other position isomers such as 5-decen-1-ol and 4-decen-1-ol. In some embodiments, the ruthenium catalyst is a ruthenium complex and the amount of the ruthenium catalyst is at least 0.001 mol %, or at least 0.002 mol %, or at least 0.005 mol %, or at least 0.01 mol %, or at least 0.02 mol % based on the total molar amount of the terminal alkene. In some embodiments, the ruthenium catalyst is a ruthenium complex and the amount of the ruthenium catalyst is no more than 0.2 mol %, or no more than 0.15 mol %, or no more than 0.1 mol % based on the total molar amount of the terminal alkene. In some embodiments, the amount of the ruthenium complex is from about 0.001 mol % to about 0.2 mol %, or from about 0.005 mol % to about 0.15 mol %, or from about 0.01 mol % to about 0.1 mol % based on the total molar amount of the terminal alkene.
- Many aspects and embodiments have been described above and are merely exemplary and not limiting. After reading this specification, skilled artisans appreciate that other aspects and embodiments are possible without departing from the scope of the invention.
- The concepts described herein will be further described in the following examples, which do not limit the scope of the invention described in the claims.
- Glassware was dried in an oven at 175° C. before use. Reactions were performed in 2 mL or 8 mL vials equipped with a magnetic stirrer and closed with a steel cap having a rubber septum part to sample out. Reagents and solvents were obtained from commercial sources and were used without further purification unless otherwise indicated. Products were characterised by GC-MS, 1H- and 13C-NMR, and DEPT (distortionless enhancement by polarization transfer). Gas chromatographic analyses were performed in an instrument equipped with a 25 m capillary column of 5% phenylmethylsilicone. N-dodecane was used as an external standard. GC/MS analyses were performed on a spectrometer equipped with the same column as the GC and operated under the same conditions. 1H, 13C and DEPT measurements were recorded in a 300 MHz instrument using CDCI3 as a solvent, containing TMS as an internal standard.
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- A mixture of two regioisomers 2-propoxy-5-vinylcyclohexan-1-ol (1a) and 2-propoxy-4-vinylcyclohexan-1-ol (1b) in 1-propanol solvent was concentrated under reduced pressure to remove the solvent. Then, the mixture (0.2-2 g) was charged into a 2 mL or 8 mL vial equipped with a magnetic stirrer and the Ru(methylallyl)2(COD) catalyst (0.0001-0.1 mol %) was added. The vial was closed with a cap, placed in a pre-heated bath oil at the reaction temperature of 150° C. under magnetically stirring and maintained during the reaction time. The product mixture comprising 2-propoxy-5-ethylidenecyclohexan-1-ol (2a) and 2-propoxy-4-ethylidenecyclohexan-1-ol (2b) was characterised by GC and NMR. Results are shown in Table 1.
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TABLE 1 Catalyst Amount Reaction Time Yield Entry (mol %) (hour) (%) 1 0.1 1 97.8 2 0.05 2.5 98.2 3 0.01 21 89.5 4 0.005 21 70.5 5 0.001 64 25.0 6 0.0005 64 15.1 7 0.0001 64 4.1 - The isomerization reactions were carried out with the terminal alkene starting material and the ruthenium catalyst alone, that is, the isomerization reactions were carried out essentially free of a solvent, an additive, an acid, and an additional ligand. This example demonstrated that Veraspice fragrance ingredients 2a and 2b can be efficiently made with high yield by using Ru(methylallyl)2(COD) as the catalyst at very low concentration in the absence of a solvent.
- Same process as Example 1 was conducted in Example 2 except that RuCl2(PPh3)3 was used as the catalyst for Example 2. The reaction temperature is also 150° C. Results are shown in Table 2.
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TABLE 2 Catalyst Amount Reaction Time Yield Entry (mol %) (hour) (%) 1 0.1 1 98.0 2 0.08 5 98.0 3 0.05 23 98.1 4 0.05 22 94.8 5 0.01 22 92.5 6 0.005 22 72.6 7 0.001 22 22.7 8 0.0005 22 12.2 9 0.0001 22 3.0 - The isomerization reactions were carried out with the terminal alkene starting material and the ruthenium catalyst alone, that is, the isomerization reactions were carried out essentially free of a solvent, an additive, an acid, and an additional ligand. This example demonstrated that Veraspice fragrance ingredients 2a and 2b can be efficiently made with high yield by using RuCl2(PPh3)3 as the catalyst at very low concentration in the absence of a solvent.
- Same process as Example 1 was conducted in Example 3 except that RuCl3 was used as the catalyst for Example 3. The reaction temperature is also 150° C. Results are shown in Table 3.
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TABLE 3 Catalyst Amount Reaction Time Yield Entry (mol %) (hour) (%) 1 0.2 6 88.8 2 0.2 6 97.0 3 0.13 6 97.9 4 0.1 6 97.7 5 0.05 6 98.4 6 0.01 22 49.6 - The isomerization reactions were carried out with the terminal alkene starting material and the ruthenium catalyst alone, that is, the isomerization reactions were carried out essentially free of a solvent, an additive, an acid, and an additional ligand. This example demonstrated that Veraspice fragrance ingredients 2a and 2b can be efficiently made with high yield by using RuCl3 as the catalyst at low concentration in the absence of a solvent.
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- Methyl eugenol (1 mL) was charged into a 2 mL or 8 mL vial equipped with a magnetic stirrer and the Ru(methylallyl)2(COD) catalyst (0.0001-5 mol %) was added. The vial was closed with a cap, placed in a pre-heated bath oil at the reaction temperature of 150° C. under magnetically stirring and maintained during the reaction time. The product mixture comprising methyl isoeugenol was characterised by GC and NMR. Results are shown in Table 4.
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TABLE 4 Catalyst Amount Reaction Yield Entry (mol %) Time (%) 1 5 1 minute 100 2 1 1 minute 100 3 0.005 4 hours 90 4 0.001 7 hours 78 5 22 hours 96 6 0.0005 21 hours 94 7 0.0001 20 hours 81 - The isomerization reactions were carried out with the terminal alkene starting material and the ruthenium catalyst alone, that is, the isomerization reactions were carried out essentially free of a solvent, an additive, an acid, and an additional ligand. This example demonstrated that methyl isoeugenol can be efficiently made with high yield by using Ru(methylallyl)2(COD) as the catalyst at very low concentration in the absence of a solvent.
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- Methyl eugenol (1 mL) was charged into a 2 mL or 8 mL vial equipped with a magnetic stirrer and a catalyst (0.01 mol %) was added. The vial was closed with a cap, placed in a pre-heated bath oil at the reaction temperature of 150° C. under magnetically stirring and maintained for one hour (reaction time). After one hour reaction time, the reaction was stopped and cooled. The product mixture was characterised by GC and NMR for the cis and trans methyl isoeugenol content. Results are shown in Table 5.
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TABLE 5 Conversion Yield (%) Entry Catalyst (%) cis trans 1 FeCl2 0.0 0.0 0.0 2 Fe(CO)5 dis. 0.1 0.0 0.0 3 Ferrocene 0.0 0.0 0.0 4 Co(NO3)2•6H2O 0.0 0.0 0.0 5 Ni(NO3)2•6H2O 0.0 0.0 0.0 6 NiCl2glyme 0.0 0.0 0.0 7 Cu(NO3)2•3H2O 0.0 0.0 0.0 8 [(iPr)CuCl] 0.0 0.0 0.0 9 Na2PdCl4•3H2O 30.7 3.4 27.3 10 RhCl3•xH2O 61.7 17.5 44.3 11 [Rh(COD)Cl]2 23.5 4.8 18.7 12 IrCl3•xH2O 17.0 2.6 14.4 13 [Ir(COD) Cl]2 28.6 3.6 25.0 14 RuCl2(PPh3)3 99.5 8.9 90.7 15 Ru(methylallyl)2(COD) 98.0 13.1 85.0 - In Table 5, “Fe(CO)5 dis.” means Fe(CO)5 previously dissolved in methyl eugenol before adding to the vial. In this experiment, the total amount of methyl eugenol fed to the vial was still 1 mL.
- The isomerization reactions were carried out with the terminal alkene starting material and the catalyst alone, that is, the isomerization reactions were carried out essentially free of a solvent, an additive, an acid, and an additional ligand. This example demonstrated that while the ruthenium catalyst got nearly quantitatively the isomerized product in just one hour reaction time, with very high selectivity and without branched nor oligomerized products, other metal catalysts were barely active under solvent- and additive-free reaction conditons.
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- Methyl eugenol (1 mL) was charged into a 2 mL or 8 mL vial equipped with a magnetic stirrer and a ruthenium catalyst (0.001 mol %) was added. The vial was closed with a cap, placed in a pre-heated bath oil at the reaction temperature of 150° C. under magnetically stirring and maintained for four hours (reaction time). After four hours reaction time, the reaction was stopped and cooled. The product mixture comprising methyl isoeugenol was characterised by GC and NMR. Results are shown in Table 6.
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TABLE 6 Conversion Yield (%) Entry Catalyst (%) cis trans 1 RuO2 0.0 0.0 0.0 2 Ru(methylallyl)2(COD) 83.9 16.5 67.4 3 RuCl2(PPh3)3 95.0 16.6 78.3 4 RuCl2(C14H16NP)2 93.7 17.0 76.8 5 Milstein 72.5 15.8 56.6 6 Gusev Ru—PNN 75.7 16.4 59.2 7 Ru(CO)H2(PPh3)3 98.3 14.9 83.3 8 Ru3(CO)12 99.4 9.2 90.2 9 Grubbs 1st 99.3 12.6 86.7 Generation 10 Grubbs 2nd97.9 15.3 82.6 Generation 11 Hoveyda- Grubbs 2nd98.8 14.0 84.8 Generation - The isomerization reactions were carried out with the terminal alkene starting material and the ruthenium catalyst alone, that is, the isomerization reactions were carried out essentially free of a solvent, an additive, an acid, and an additional ligand. This example demonstrated that methyl isoeugenol can be efficiently made with high yield by using ruthenium complexes at 0.001 mol% (10 ppm) amount in the absence of a solvent.
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- Methyl eugenol (1 mL) was charged into a 2 mL or 8 mL vial equipped with a magnetic stirrer and a ruthenium catalyst comprising ruthenium supported on a catalyst support (supported ruthenium catalyst) was added. The vial was closed with a cap, placed in a pre-heated bath oil at the reaction temperature of 150° C. under magnetically stirring and maintained during the reaction time. The supported ruthenium catalysts were either commercial or prepared by impregnation of aqueous RuCl3. The product mixture comprising methyl isoeugenol was characterised by GC and NMR. Results are shown in Table 7.
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TABLE 7 Catalyst Amount Reaction Time Yield Entry Catalyst (mol % Ru) (hour) (%) 1 Ru on silica 0.005 1 99.0 (5 wt % Ru) 2 Ru on TiO2 0.1 17 97.7 (5 wt % Ru) 3 Ru on alumina 0.1 17 89.3 (3 wt % Ru) 4 Ru on alumina 0.2 20 88.2 (5 wt % Ru) 5 Ru on carbon 0.1 18 81.0 (5 wt % Ru) 6 Ru on KY 0.01 22 95.3 (1 wt % Ru) - In Table 7, “wt % Ru” means the amount of ruthenium supported on the catalyst support based on the total weight of the supported ruthenium catalyst, “mol % Ru” means the amount of ruthenium supported on the catalyst support comparing with the total molar amount of the terminal alkene, and KY means zeolite Y with potassium.
- The isomerization reactions were carried out with the terminal alkene starting material and the supported ruthenium catalyst alone, that is, the isomerization reactions were carried out essentially free of a solvent, an additive, an acid, and an additional ligand. This example demonstrated that methyl isoeugenol can be efficiently made with high yield by using supported ruthenium catalysts at very low ruthenium concentration in the absence of a solvent.
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- In Scheme 7, the broken line represents one double bond and six single bonds.
- 9-decen-1-ol (1 mL) was charged into a 2 mL or 8 mL vial equipped with a magnetic stirrer and the Ru(methylallyl)2(COD) catalyst (0.0001-0.1 mol %) was added. The vial was closed with a cap, placed in a pre-heated bath oil at the reaction temperature of 150° C. under magnetically stirring and maintained during the reaction time. The product mixture comprising isomers x-decen-1-ol (x is an integer from 2 to 8) was characterised by GC and NMR. Results are shown in Table 8.
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TABLE 8 Cat. GC Peak Area of x-decen-1-ol Isomers En- (mol T Yield x = x = try %) (h) (%) 2 x = 3 x = 4 x = 5 x = 6 x = 7 8 1 0.1 1 97 2.2 5.8 27.6 27.6 23.3 9.75 33.0 2 0.05 2 97 2.0 3.8 21.9 30.4 27.0 11.1 38.1 3 0.01 3 96 1.0 3.3 21.8 28.5 29.5 14.2 43.7 4 0.005 4 96 0.8 1.9 18.0 27.5 34.1 16.4 50.5 5 0.001 22 95 0.5 0.2 8.2 28.2 44.6 18.3 62.9 6 0.0005 22 95 0.5 0.0 5.0 26.0 47.5 21.0 68.5 7 0.0001 22 91 0.5 0.0 8.3 14.3 51.0 25.8 76.8 - In Tables 8, 9 and 10, “Cat. (mol %)” means the amount of Ru(methylallyl)2(COD) catalyst in mol % based on the total molar amount of the terminal alkene, and “T (h)” means reaction time in hours.
- The isomerization reactions were carried out with the terminal alkene starting material and the ruthenium catalyst alone, that is, the isomerization reactions were carried out essentially free of a solvent, an additive, an acid, and an additional ligand. This example demonstrated that isorosalva fragrance intermediates can be efficiently made with high yield by using Ru(methylallyl)2(COD) as the catalyst at very low concentration in the absence of a solvent.
- Same process as Example 8 was conducted in Example 9 except that the reaction temperature is 175° C. in this Example. Results are shown in Table 9.
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TABLE 9 Cat. GC Peak Area of x-decen-1-ol Isomers En- (mol T Yield x = x = x = x = x = try %) (h) (%) 2 x = 3 x = 4 5 6 7 8 1 0.01 0.5 96 1.5 7.6 30.6 27.0 19.2 8.2 27.4 2 0.005 0.5 96 1.1 5.40 29.0 29.6 22.7 9.7 32.4 3 0.001 1 96 0.4 1.7 21.0 33.4 30.2 12.8 43.0 4 0.0005 1 95 0.4 0.8 15.4 33.7 35.0 14.7 49.7 5 0.0001 22 94 0.4 0.0 5.5 13.5 56 24.5 80.4 - The isomerization reactions were carried out with the terminal alkene starting material and the ruthenium catalyst alone, that is, the isomerization reactions were carried out essentially free of a solvent, an additive, an acid, and an additional ligand. This example demonstrated that isorosalva fragrance intermediates can be efficiently made with high yield by using Ru(methylallyl)2(COD) as the catalyst at very low concentration in the absence of a solvent. In Entry 1 where the amount of the Ru(methylallyl)2(COD) catalyst was 0.01 mol %, about 3 mol % decanal was formed.
- Same process as Example 8 was conducted in Example 10 except that the reaction temperature is 200° C. in this Example. Results are shown in Table 10.
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TABLE 10 Cat. GC Peak Area of x-decen-1-ol Isomers En- (mol Yield x = x = x = try %) T (h) (%) 2 3 x = 4 x = 5 x = 6 x = 7 8 1 0.01 0.5 98 1.8 8.4 30.5 27.0 17.7 7.8 25.5 2 0.005 0.5 96 1.3 6.4 29.6 30.1 21.8 9.6 31.4 3 0.001 0.5 96 0.8 3.3 24.2 33.3 26.0 11.5 37.5 4 0.0005 1 96 0.7 2.2 21.6 33.6 28.7 12.8 41.5 5 0.0001 22 94 0.5 1.0 6.0 15.1 51.0 24.0 75.0 - The isomerization reactions were carried out with the terminal alkene starting material and the ruthenium catalyst alone, that is, the isomerization reactions were carried out essentially free of a solvent, an additive, an acid, and an additional ligand. This example demonstrated that isorosalva fragrance intermediates can be efficiently made with high yield by using Ru(methylallyl)2(COD) as the catalyst at very low concentration in the absence of a solvent. In Entry 1 where the amount of the Ru(methylallyl)2(COD) catalyst was 0.01 mol %, about 6 mol % decanal was formed.
- Note that not all of the activities described above in the general description or the examples are required, that a portion of a specific activity may not be required, and that one or more further activities may be performed in addition to those described. Still further, the order in which activities are listed are not necessarily the order in which they are performed.
- In the foregoing specification, the concepts have been described with reference to specific embodiments. However, one of ordinary skill in the art appreciates that various modifications and changes can be made without departing from the scope of the invention as set forth in the claims below. Accordingly, the specification is to be regarded in an illustrative rather than a restrictive sense, and all such modifications are intended to be included within the scope of invention.
- Benefits, other advantages, and solutions to problems have been described above with regard to specific embodiments. However, the benefits, advantages, solutions to problems, and any feature(s) that may cause any benefit, advantage, or solution to occur or become more pronounced are not to be construed as a critical, required, or essential feature of any or all the claims.
- It is to be appreciated that certain features are, for clarity, described herein in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features that are, for brevity, described in the context of a single embodiment, may also be provided separately or in any subcombination.
Claims (15)
1. A process for making fragrance ingredient or fragrance intermediate, comprising: isomerizing a starting material comprising a terminal alkene to form a product comprising an internal alkene in the presence of a ruthenium catalyst at a temperature of at least about 120° C.
3. The process of claim 1 , wherein the temperature is in a range of from about 120° C. to about 250° C.
4. The process of claim 1 , wherein the ruthenium catalyst is a ruthenium complex.
5. The process of claim 4 , wherein the amount of the ruthenium catalyst is in a range of from about 0.0001 mol % to about 0.2 mol % based on the total molar amount of the terminal alkene.
6. The process of claim 1 , wherein the ruthenium catalyst is a ruthenium salt.
7. The process of claim 6 , wherein the amount of the ruthenium catalyst is in a range of from about 0.01 mol % to about 1 mol % based on the total molar amount of the terminal alkene.
8. The process of claim 1 , wherein the ruthenium catalyst is selected from the group consisting of ruthenium complexes, ruthenium salts, ruthenium in metal form, and mixtures thereof.
9. The process of claim 1 , wherein the ruthenium catalyst is selected from the group consisting of bis(2-methylallyl)(1,5-cyclooctadiene)ruthenium(II) complex (Ru(methylallyl)2(COD)), dichlorotris(triphenylphosphine)ruthenium(II) complex (RuCl2(PPh3)3), and RuCl3.
10. The process of claim 1 , wherein the terminal alkene is a mixture of 2-propoxy-5-vinylcyclohexan-1-ol and 2-propoxy-4-vinylcyclohexan-1-ol, and the internal alkene is a mixture of 2-propoxy-5-ethylidenecyclohexan-1-ol and 2-propoxy-4- ethylidenecyclohexan-1-ol.
11. The process of claim 1 , wherein the terminal alkene is methyl eugenol and the internal alkene is methyl isoeugenol.
12. The process of claim 1 , wherein the terminal alkene is 9-decen-1-ol and the internal alkene comprises a mixture of 6-decen-1-ol, 7-decen-1-ol and 8-decen-1-ol.
13. The process of claim 1 , wherein the isomerizing step is conducted in the absence of a solvent.
14. The process of claim 1 further comprising recovering the internal alkene.
15. The process of claim 1 , wherein the temperature is in a range of from about 130° C. to about 240° C.
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EP21382234 | 2021-03-23 | ||
EP21382234.9 | 2021-03-23 | ||
PCT/US2022/020979 WO2022203964A2 (en) | 2021-03-23 | 2022-03-18 | Selective catalytic alkene isomerization for making fragrance ingredients or intermediates |
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US20240182393A1 true US20240182393A1 (en) | 2024-06-06 |
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US18/282,838 Pending US20240182393A1 (en) | 2021-03-23 | 2022-03-18 | Selective catalytic alkene isomerization for making fragrance ingredients or intermediates |
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US (1) | US20240182393A1 (en) |
EP (1) | EP4313926A2 (en) |
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US4575575A (en) | 1984-04-05 | 1986-03-11 | Phillips Petroleum Company | Catalysts and process for olefin conversion |
US4992613A (en) | 1989-08-16 | 1991-02-12 | Shell Oil Company | Double-bond isomerization process using basic zeolite catalysts |
US5043520A (en) | 1989-12-21 | 1991-08-27 | Shell Oil Company | Concurrent isomerization and disproportionation of olefins |
US5237120A (en) | 1991-12-27 | 1993-08-17 | Mobil Oil Corporation | Double bond isomerization of olefin-containing feeds with minimal oligomertization using surface acidity deactivated zeolite catalysts |
EP3071538B1 (en) | 2013-11-20 | 2021-02-17 | Lummus Technology LLC | Olefin double bond isomerization catalyst with high poison resistance |
US9434669B2 (en) * | 2014-07-21 | 2016-09-06 | International Flavors & Fragrances Inc. | Cyclohexanols and their use in perfume compositions |
CN112110807A (en) * | 2019-06-19 | 2020-12-22 | 成都三香汇香料有限公司 | Method for synthesizing vanillin by oxidizing eugenol with ozone |
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- 2022-03-18 WO PCT/US2022/020979 patent/WO2022203964A2/en active Application Filing
- 2022-03-18 CN CN202280023356.XA patent/CN117083259A/en active Pending
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WO2022203964A3 (en) | 2022-12-08 |
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CN117083259A (en) | 2023-11-17 |
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